Tertiary alcohols

ABSTRACT

The invention relates to tertiary alcohols of the formula I ##STR1## wherein R 1 , A 1 , Z 1 , m, A 2 , Y, Q 1 , Q 2 , Q 3  and Z 2  have the meanings indicated in claim 1, and also to a process for the preparation of these compounds.

This application is a continuation of application Ser. No. 07/133,109,filed as PCT/EP87/00132 on Mar. 7, 1987, published as WO87/05599 Sept.24, 1987, now abandoned.

The invention relates to tertiary alcohols of the formula I ##STR2##wherein R¹ is halogen or alkyl which has 1-15 C atoms and in which oneor two non-adjacent CH₂ groups can be replaced by 0 atoms and/or --CO--groups and/or --CO--O-- groups and/or --CH═CH-- groups, or, in the eventthat Y is H or CN, R¹ is also H,

A¹ is 1,4-phenylene or 1,4-cyclohexylene which is unsubstituted ormonosubstituted or polysubstituted by halogen and/or CH₃ groups,

Z¹ is --CH₂ CH₂ --, --CH₂ O--, --OCH₂ -- or a single bond,

m is 0, 1 or 2,

A² is 1,4-phenylene which is unsubstituted or monosubstituted orpolysubstituted by halogen and/or CH₃ groups, ##STR3## Z² is --COOR or--CN, Q³ is alkylene having 1-15 C atoms, alkylidene having 2-15 Catoms, an aromatic system or a single bond,

Y is H, CN or R and

R is alkyl having 1-15 C atoms,

and Q² a nd Q³ are not both simultaneously a single bond and to metalalcoholates thereof and to a process for the preparation of thesecompounds.

Tertiary alcohols of the formula I are of great interest as intermediateproducts for the preparation of liquid-crystal compounds.

Readily accessible intermediate products from which the correspondingsubstances having liquid-crystal properties can be obtained in as fewstages of synthesis as possible are required for the preparation ofliquid-crystal substances.

It was the object of the present invention to find appropriately readilysynthesizable intermediate products for the preparation of liquidcrystals and also a process for their preparation.

This object has been achieved by providing the tertiary alcohols of theformula I and a process for their preparation.

All the processes hitherto known for the preparation of similarcompounds of the formula I lead to unsatisfactory results. The factorsresponsible for this are, above all, poor yields and in some casesstarting compounds which are difficult of access.

Para-substituted phenylcyclohexanecarboxylic acids and their esters areprepared, for example, by reacting cyclohexene with acetylchloride/AlCl₃ and with benzene, followed by haloform degradation of theketone to the carboxylic acid (described in J. Amer. Chem. Soc. 67, 1045(1945), W.S. Johnson et al. and by Nenitzescu et al., Ann. 519 (260)1935). The substituent in the p-position, for example OCH₃, must then beintroduced by electrophilic aromatic substitution (for examplenitration, reduction, diazotization, introduction of the OH group andmethylation), which is a very involved route.

A further example describes the process for the preparation of4-[4-(trans-4-alkylcyclohexyl)-phenyl]-cyclohexanecarboxylic acids(according to EP 90,671) by reducing4-[trans-4-alkylcyclohexyl]biphenyl-4-carboxylic acid with metallicsodium in isoamyl alcohol. The disadvantages of this process are a veryhigh consumption of reducing agent and relatively low yields. A processis also known for the preparation of compounds of the formula I,described in J. Org. Chem. 39, 2787, in which corresponding Grignardcompounds are reacted with cyclohexanones. Undesirable side reactions(such as, for example, aldol reactions between the carbonyl compounds)often take place in this process, however.

Products similar to the compounds of the formula I are also described,for example, in German Patent Specification 2,701,591. In this patent4-alkylcyclohexanones are reacted with aromatic Grignard compounds.

However, this process is not possible for the preparation of thetertiary alcohols of the formula I, since Grignard compounds wouldattack both the keto group on the cyclohexanone and also the CN or estergroup present in the p-position. In the case of reaction with Grignardcompounds, it would be necessary to re-introduce a substituent of thistype subsequently.

It was therefore the object of the present invention also to find aprocess for the preparation of the compounds of the formula I which doesnot have the disadvantages described in the present processes or hasthese disadvantages only to a slight extent.

It has been found, surprisingly, that organozirconium or organotitaniumcompounds are excellently suitable for the preparation of compounds ofthe formula I.

The invention therefore relates to the compounds of the formula I',##STR4## wherein R¹, A¹, Z¹, m, A², Y, Q³ and Z² have the meaningsindicated and W is ##STR5## in which Q¹ and Q² have the meaningsindicated, in particular to the tertiary alcohols of the formula I andmetal alcoholates thereof and to a process for the preparation ofcompounds of the formula I, characterized in that a keto compound of theformula II ##STR6## wherein Q¹, Q², Q³, Y, Z² and R have the meaningsindicated above, is reacted with an appropriate aryltitanium trialkoxideor arylzirconium trialkoxide.

The invention also relates to the use of the compounds of the formula Ias intermediate products for the preparation of liquid crystals.

For the sake of simplicity, in what follows, Phe is a 1,4-phenylenegroup which is unsubstituted or monosubstituted or polysubstituted byhalogen and/or CH₃ groups, Cy is a 1,4-cyclohexylene group which isunsubstituted or monosubstituted or polysubstituted by halogen and/orCH₃ groups, and X is the group ##STR7##

The compounds of the formula I accordingly embrace the compounds of thepartial formula Ia (in the case where m=0), Ib to Ic (where m=1) and Idto Ig (where m=2): ##STR8##

The compounds of the partial formula Ib preferably embrace those of thepartial formulae Iba and Ibb: ##STR9##

The compounds of the partial formula Ic preferably embrace those of thepartial formulae Ica to Icf: ##STR10##

The compounds of the partial formula Id preferably embrace those of thepartial formulae Ida to Idd: ##STR11##

The compounds of the partial formula Ie preferably embrace those of thepartial formulae Iea to Ied: ##STR12##

The compounds of the partial formula If preferably embrace those of thepartial formulae Ifa to Ifd: ##STR13##

The compounds of the partial formula Ig preferably embrace those of thepartial formulae Iga to Igd: ##STR14##

In the preceding and following formulae partial formulae R¹ ispreferably an alkyl group which has 1-15 C atoms and in which one or twonon-adjacent CH₂ groups can also be replaced by 0 atoms and/or --CO--groups and/or --CO--O-- groups and/or --CH═CH-- groups. If Y is H or CN,R¹ can also be H.

A² is preferably unsubstituted 1,4-phenylene and also 1,4-phenylenewhich is monosubstituted by halogen. A suitable halogen is preferably F,Cl or Br, especially F.

M is preferably 1 or 2, especially 1.

Z has primarily the meaning of a single bond, secondarily Z¹ is --CH₂CH₂ -- and also --OCH₂ -- or --CH₂ O--.

A¹ is preferably unsubstituted 1,4-phenylene or 1,4-cyclohexylene. Ifthese groups are present in a substituted form, monosubstitution by F,Cl or Br, preferably monosubstitution by fluorine, is preferred.

The alicyclic fragment ##STR15## can consist of monocyclic, dicyclic orbicyclic (sic) rings or of several rings, including fused rings, of anydesirable size. Amongst these, the following alicyclic fragments arevery particularly preferred: ##STR16##

In the preceding and following formulae Q³ is alkylene having 1 to 15 Catoms, preferably 1-10 C atoms and particularly 1-5 C atoms, andaccordingly is preferably methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene or decylene, or isalso alkylidene having 2-15 C atoms, preferably 2-7 C atoms, andaccordingly is preferably ethylidene, propylidene, butylidene,pentylidene, hexylidene or heptylidene and also octylidene, nonylideneor decylidene.

Q³ is also an aromatic system or a single bond, which is particularlypreferred. However, Q² and Q³ are not simultaneously a single bond.

Z² is --COOR or --CN, preferably an ester group.

R is alkyl having 1-15 C atoms, preferably having 3-15 C atoms andparticularly preferably having 5-15 C atoms.

Y is H, CN or R, preferably H. R has the meaning given above.

In the preceding and following formulae R or R¹ is preferably linear orbranched alkyl having 1-15 C atoms, preferably 2-10 C atoms, andaccordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl or decyl, and also methyl, undecyl, dodecyl, tridecyl,tetradecyl or pentadecyl. Branched radicals such as isopropyl, 2-butyl,isopentyl, 1-methylpentyl, 2-methylpentyl, 1-methylhexyl or1-methylheptyl are also preferred. R¹ is preferably also ethoxy,propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy ordecyloxy, and also methoxy, undecyloxy, dodecyloxy, tridecyloxy,tetradecyloxy or pentadecyloxy or isopropoxy, isopentyloxy, 2-butoxy or1-methylpentyloxy. The Rs in Y and COOR can be identical or different.

The process according to the invention starts from the readilyaccessible aryl halides. These are converted by known methods intoGrignard reagents or lithiated, and the reaction with a chlorotrialkylorthotitanate or orthozirconate to give the corresponding aryltitaniumtrialkoxide or arylzirconium trialkoxide is then carried out.

This reaction is preferably carried out in an inert solvent, such as,for example, tetrahydrofuran, diethyl ether, benzene, toluene, hexaneand others, or in suitable mixtures of these solvents and attemperatures from -78° C. to 100° C., preferably at -15° C. to 50° C.

The corresponding keto compound is then added, also in one of the inertsolvents mentioned above and at the temperatures indicated. Theorganometallic compound then adds on selectively to the keto group (cf.Angew. Chem. 95, 12 (1983)) to give the corresponding metal alcoholate,in which the metal present is, for example, magnesium, lithium, titaniumor zirconium. This alcoholate is then converted in a customary mannerinto the corresponding tertiary alcohol, which can be dehydratedreadily. The compounds of the formula I obtained in this way can be usedfor the synthesis of liquid-crystal compounds and can readily beprocessed further to give a very wide variety of end products, e.g., byhydrogenation to give the correspondingly saturated rings, bydehydrogenation to give aromatic compounds, by elimination of water togive compounds of the formula IV ##STR17## and, if appropriate, bysubsequent hydrogenation to give compounds of the formula V. ##STR18##

It is also possible to saponify corresponding esters (Z² =COOR) ornitriles to give the corresponding acids and, if appropriate, to attachthe latter to further rings.

It is also possible to introduce further substituents into the compoundsof the formulae I, IV or V.

There are thus many possibilities available for preparing furtherliquid-crystal products in a simple manner from the tertiary alcohols ofthe formula I.

The compounds of the formula IV are also novel and are therefore also asubject of the invention.

The starting compounds employed are keto compounds of the formula II andaryl halides of formula VI

    R.sup.1 --(A.sup.1 --Z.sup.1).sub.m --A.sup.2 -Halogen     VI

wherein R¹, A¹, Z¹, m and A² have the meaning indicated in formula I andhalogen is fluorine, chlorine, iodine or bromine. It is preferable temploy the corresponding bromides, and also the chlorides or iodides.

The formulae VIa to VIt constitute a group of very particularlypreferred starting compounds: ##STR19##

Suitable keto compounds which can be employed are any desired cyclicketo esters or keto nitriles of the formula II ##STR20##

In this formula Y, Q³ and Z² have the preferred meanings indicated.

All the structures described, especially the preferred structures of theformulae IIIa to IIIi are suitable for the alicyclic fragment ##STR21##

The trialkoxychloro compounds, in particular chlorotitanium orchlorozirconium triisopropoxide are preferably employed as theorganozirconium or organotitanium reagent. In this regard, theorganotitanium compounds are preferred.

The process according to the invention can therefore be applied to anydesired cyclic keto esters, with the exception of β-keto esters, ketonitriles and the corresponding arylhalides which can be converted intoan organometallic compound.

Hence intermediate products and a process for their preparation, whichstarts from readily accessible starting materials and affords, in goodyields, a large number of structures, have been found.

The compounds of the formula I are of great interest as intermediateproducts for the preparation of liquid-crystal compounds.

The keto compounds of the formula II employed as starting compounds arein part known, for example the compounds VIIa or VIIb, which aredescribed in German Offenlegungsschrift 3,407,113: ##STR22##

However, formula II also embraces new compounds of the formula II'##STR23## wherein R² is alkyl having 2-15 C atoms, Y has the meaningindicated above and R³ is CN or COOR⁴, which are also a subject of theinvention. In these compounds R⁴ is alkyl having 3-15 C, preferably5-15,C atoms.

The compounds of the formula II' can be prepared by generally knownmethods of organic chemistry.

The following examples are intended to illustrate the invention ingreater detail, without limiting it. m.p.=melting point. In thepreceding and following text percentages are percent by weight; thetemperatures are quoted in degrees Centigrade.

EXAMPLE 1

A solution of 0.1 M TiCl[OCH(CH₃)₂ ]₃ in 50 ml of THF is added at 40° toa Grignard reagent prepared from 0.1 M 4-bromoanisole in 100 ml of THFand 0.11 M magnesium turnings in 20 ml of THF, and the mixture isstirred for 30 minutes. 0.1 M ethyl cyclohexanone-4-carboxylate in 50 mlof THF is then added at 30-40°, and the reaction mixture is stirred forseveral hours The tertiary alcohol formed can either be isolated in acustomary manner or can be dehydrated immediately afterwards withoutisolation.

500 ml of H₂ O and 50 ml of hydrochloric acid are added, the mixture isextracted with 250 ml of TBM, the extract is washed and evaporated andthe substance is purified by means of chromatography over silica gel (intoluene, eluted with acetone), and is then heated withethanol/hydrochloric acid, the mixture is evaporated and the product iswashed and filtered off to give, after recrystallization, ethyl4-(4-methoxyphenyl)-cyclohexenecarboxylate.

The following dehydrated products are prepared analogously via thecorresponding tertiary alcohols

methyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

propyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

butyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

pentyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

hexyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

isopropyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

2-methylpentyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

1-methylheptyl 4-(4-methoxyphenyl)-cyclohexenecarboxyoxylate

octyl 4-(4-methoxyphenyl)-cyclohexenecarboxylate

methyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

ethyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

propyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

butyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

pentyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

hexyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

isopropyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

2-methylpentyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

1-methylheptyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

octyl 4-(4-chlorophenyl)-cyclohexenecarboxylate

methyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

ethyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

propyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

butyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

pentyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

hexyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

isopropyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

2-methylpentyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

1-methylheptyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

octyl 4-(4-pentylphenyl)-cyclohexenecarboxylate

methyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

ethyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

propyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

butyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexpentyl

pentyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

hexyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

isopropyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

2-methylpentyl4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

1-methylheptyl4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

octyl 4-[4-(trans-4-propylcyclohexyl)-phenyl]-cyclohexenecarboxylate

nethyl4-[4'-(trans-4-pentylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

ethyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

propyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

butyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

pentyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

hexyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

isopropyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

2-methylpentyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

1-methylheptyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

octyl4-[4'-(trans-4-propylcyclohexyl)-biphenyl-4-yl]-cyclohexenecarboxylate

methyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

ethyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

propyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

butyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

pentyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

hexyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

isopropyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

2-methylpentyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

1-methylheptyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

octyl 4-(4'-pentoxybiphenyl-4-yl)-cyclohexenecarboxylate

methyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

ethyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

propyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

butyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

pentyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

hexyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

isopropyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

2-methylpentyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

1-methylheptyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

octyl 4-(4-methoxyphenyl)-bicyclohexene-4'-carboxylate

methyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

ethyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

propyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylatebutyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

pentyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

hexyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

isopropyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

2-methylpentyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

1-methylheptyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

octyl6-(4-pentylphenyl)-1,2,3,4,5,8,9,10-octahydronaphthaline-2-carboxylate

EXAMPLE 2

788 ml of a 1.6 molar solution of butyllithium in n-hexane are added at-15° C. and with the exclusion of atmospheric oxygen and moisture to 462g of 4-bromo-4'-n-octyloxybiphenyl in 1.4 1 of toluene and 150 ml ofTHF.

After stirring for approx. 15 minutes, 313 g of chlorotriisopropylorthotitanate in 380 ml of toluene containing 40 ml of THF are added,also at -15° C.

After stirring for a further 15 minutes, 228 g of ethylcyclohexanecarboxylate in 600 ml of toluene are added at -15° C., andthe mixture is stirred overnight while it slowly warms up to roomtemperature. 2 l of 1 N HCl are then added all at once to the reactionmixture. The whole reaction mixture is then filtered through a suctionfilter covered with a dry layer of Celite. The organic phase of thefiltrate is separated off, dried and concentrated. The residue is takenup in toluene, and the non-polar byproducts are removed over a silicagel column, using toluene. The ethyl1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate is thenwashed off the column by means of methanol or acetone and is isolated byevaporation.

The following are prepared analogously:

methyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-octyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-heptyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-hexyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-pentyloxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-butoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-propoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-ethoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

ethyl 1-hydroxyl-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-methoxybiphenyl-4'-yl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-octyloxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-heptyloxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-hexyloxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-pentyloxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-butoxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-propoxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylcte

ethyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-ethoxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-methoxyphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1(4-octylphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

propyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

butyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

pentyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

hexyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

heptyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

octyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexan-4-carboxylate

methyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

ethyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

propyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

butyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

pentyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

hexyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

heptyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

octyl 1-hydroxy-1-(4-hexylphenyl)-cyclohexan-4-carboxylate

methyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexan-4-carboxylate

ethyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexan-4-carboxylate

propyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexan-4-carboxylate

butyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexan-4-carboxylate

octyl 1-hydroxy-1-(4-octylphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-heptylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-pentylphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-butylphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-propylphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-ethylphenyl)-cyclohexane-4-carboxylate

methyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

ethyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

propyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

butyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

pentyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

hexyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

heptyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

octyl 1-hydroxy-1-(4-methylphenyl)-cyclohexane-4-carboxylate

We claim:
 1. A tertiary alcohol of the Formula I ##STR24## and thecorresponding dehydrated compounds of the Formula IV ##STR25## whereinR¹ is halogen, or if n-1, m=1 or both n and m=1, R¹ can also be alkylhaving 1-15 C atoms in which one CH₂ group can be replaced by O, --CO--,--CO--O--, or --CH═CH--;A¹ is 1,4-phenylene or 1,4-cyclohexylene whichis unsubstituted or monosubstituted or polysubstituted by halogen, CH₃,or combinations thereof; Z¹ is --CH₂ CH₂ --, --CH₂ O--, --OCH₂ --, or asingle bond; m is 0, 1, or 2; n is 0 or 1; A² is 1,4-phenylene which isunsubstituted, substituted or monosubstituted or polysubstituted byhalogen, CH₃, or combinations thereof; Z² is --COOR or --CN; Q³ isalkylene having 1-15 C atoms, alkylidene having 2-14 C atoms, or asingle bond; Y is H, CN, or R; and R is alkyl having 1-15 C atomsandmetal alcoholates of the compounds of Formula I.
 2. A compound asclaimed in claim 1, wherein n is 1, m is 1, or both n and m are 1 and R¹is an alkyl group which has 1-15 C atoms and in which one CH₂ group canbe replaced by O and/or --CO--O--.
 3. A compound as claimed in claim 1wherein A² is a 1,4-phenylene which is unsubstituted or monosubstitutedby halogen.
 4. A compound as claimed in claim 1, wherein m is 0 or
 1. 5.A compound as claimed in claim 1, wherein A¹ is 1,4-cyclohexylene or1,4-phenylene which are unsubstituted or monosubstituted by halogen. 6.A compound as claimed in claim 1, wherein n=0.
 7. A compound as claimedin claim 1, wherein Z¹ is --CH₂ CH₂ -- or a single bond.
 8. A compoundas claimed in claim 1, wherein Q³ is alkylene having 1-15 C atoms or asingle bond.
 9. A compound as claimed in claim 1, wherein Z² is --COOR.